Process for the quaternization of basic dyestuffs

ABSTRACT

Process for the production of basic dyestuffs of the formula   BY QUATERNIZING DYE BASES OF THE FORMULA IN THE PRESENCE OF ALKALINE AGENTS WHEREIN THE IMPROVEMENT COMPRISES ADDING AS ALKALINE AGENTS TERTIARY AMINES WHICH ARE SPACE OCCUPYING SUBSTITUTED ON THE NITROGEN ATOM. In the formulas given R represents the residual constituent of a 5- or 6-membered heterocyclic ring; R1 and R2 are alkyl, cycloalkyl or aralkyl and R1 can additionally be aryl; A is an aromatic or heterocyclic radical and X is an anion. The compounds are used as basic dyestuffs.

United States Patent 1 Lehment et al.

[ Feb. 27, 1973 PROCESS FOR THE QUATERNIZATION OF BASIC DYESTUFFS [75]Inventors: Klaus-Friedrich Lehment, Union, N.J.; Roderich Raue,Leverkusen, Germany [73] Assignee: Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany [22] Filed: June 25, 1969 [21]Appl. No.: 836,635

[30] Foreign Application Priority Data July 3, 1968 Germany ..P 17 70782.3

[52] US. Cl. ..260/l65, 260/154, 260/208 [51] Int. Cl. ..C09b 43/00,D06p 3/76 [58] Field of Search ..260/154, 165, 146, 157

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,132,135 6/1962Germany 1,205,638 11/1965 Germany Primary Examiner--Floyd D. I-IigelAtt0mey-Plumley & Tyner [57] ABSTRACT Process for the production ofbasic dyestuffs of the formula by quatemizing dye bases of the formula 5Claims, No Drawings PROCESS FOR THE QUATERNIZATION F BASIC DYESTUFFSFrom French Pat. specification No. 1,214,896 a process is known for theproduction of basic dyestuffs of the general formula (I) in which Rrepresents the residual constituent of a 5- or 6-membered heterocyclicring, R, denotes an alkyl, cycloalkyl, aralkyl or aryl radical, Rdenotes an alkyl, cycloalkyl or aralkyl radical, A represents anaromatic or heterocyclic radical, and X denotes an acid radical.

This process is characterized by reacting dye bases of the generalformula (II) R; (II) In the formulas (III), (IV) and (V) R, R A and Xhave the same meaning as that given in formula (I).

A large number of suitable heterocycles of the formula (III) as well asof suitable amines on which the diazonium salts (IV) are based, isdescribed in French Pat. specification No. 1,214,896.

However, the quaternization of the dye bases (II) proceeds incompletelyand with unsatisfactory yields if dye bases and alkylating agents areused in a technically pure form. When the reaction mixtures of thequaternization are worked up in the technically customary manner via theaqueous phase with acid reaction, the unreacted portion of the dye bases(II) is protonated to form the dye salts (V). In comparison with thepure dyestuffs, the dyestuffs (I) which are contaminated with the dyesalts (V) exhibit substantial disadvantages; they yield, for example, onmaterials of polyacrylonitrile duller dyeings with lesser fastness tolight and sublimation. It is not advisable to deprotonate the dye salts(V) to give the water-insoluble dye bases (II) by a correspondingincrease of the pH value, since the dyestuffs (I) form water-insolublecarbinol bases at only slightly increased pH values, which moreoverdecompose at temperatures of 60C and above. The separation of the dyebases (II) which are generally strongly contaminated, and thedecomposition reactions which partly occur already duringquaternization, lead to the above-mentioned losses in yield.

It has now been bound that the quaternization of the dye bases (II) onthe azo nitrogen linked with the radical A by means ofquaternizingagents, preferably alkylating agents, in the presence ofalkaline agents, proceeds almost completely and with very good yieldswhen tertiary amines are used as alkaline agents which are spaceoccupying-substituted on the nitrogen atom.

Space occupying-substituted tertiary amines, in the meaning of theinvention, are tertiary amines which can not substantially be alkylatedor not at all. In particular, those tertiary amines are of advantage inwhich the space occupying substitution is achieved by two substituentsof the formula in which m 0 or 1 end, in the base where m is 1, R standsfor an alkyl radical, R for an alkyl radical or for a hydroxy group, andR stands for hydrogen or for an alkyl radical and, in the case where nis 0, R and R stand for alkyl radicals, and R stands for hydrogen. If R;and R stand for alkyl radicals, then these radicals may also be aconstituent of a carbocyclic ring system which may be substituted andwhich preferably consists of five or six ring members; R, then standsfor hydrogen.

The third substituent of the above-mentioned preferred tertiary aminesis an unbranched C C alkyl radical, a B-hydroxy-propyl radical or aradical of the formulas (VIII) wherein n is an integer from 1 5, and thefree linkages of the nitrogen are occupied by substituents of theformula (VI).

Suitable tertiary amines of the above type which may be employed for thequaternization of the dye bases (II) are, for example, the followingamines or mixtures thereof:

N-me'thylor N-ethylor N-n-propylor N-n-butyl- N,N-diisopropylamine,N-methylor N-ethylor N-npropylor N-n-butyI-N,N-diisobutylamine,N-methylor N-ethylor N-n-propylor N-n-butyl-N-isopropyl-N-isobutylamine, N-methylor N-ethylor N-n-propylorN-n-butyl-N,N-bis-(2-methyl-butyl)-amine, N-methylor NoethylorN-n-propylor N-n-butyl-N,N-bis-(2,2- dimethylpropyl)-amine, N-methylorN-ethylor N-npropylor N-n-butyl-N,N-dicyclopentylamine, N- methylorN-ethylor N-n-propylor N-butyl-N,N-dicyclohexylamine,N,N,N-triisopropanolamine, N-2- hydroxypropyl-N,N-diisobutylamine,N-Z-hydroxypropyl-N-isopropyl-N-isobutylamine, N-Z-hydroxtylenediamine,N,N-tetra-cyclohexyl-butylenediamine, N,N'-tetraisopropyland N,N-tetraisobutyl-pentylenediamine, N,N'-diisopropyl-N,N-diiso-butyl-pentylenediamine, N,N'-tetra-(2-methyl-butyl)-pentylenediamine, N,N'-tetra-(2,2-dimethylpropyl)-pentylenediamine, N,N-tetracyclopentyl-pentylenediamine,N,N'-tetra-cyclohexylpentylene-diamine, N,N-tetraisopropyland N,N-tetraisobutyl-hexylene-diamine, N,N'-diisopropyl- N,N'-diisobutyl-hexylenediamine, N,N'-tetra-( 2-methylbutyl)-hexylenediamine, N,N-tetra-(2,2-dimethyl-propyl)-hexylenediamine, N,N -tetracyclopentyl-hexylenediamine,N,N'-tetra-cyclohexylhexylenediamine, l,3-bis-( diisopropylamino)-2-hydroxy-propane, 1,3-bis-(diisobutylamino)-2-hydroxy-propane,l,3-bis-[di-(Z-methyl-butyl)-amino]-2- hydroxypropane,l,3-bis-(dineopentylamino)-2- hydroxy-propane,1,3-bis-(dicyclo-pentylamino)-2- hydroxy-propane, 1,3-bis-(dicyclohexylamino)-2- hydroxy-propane, l ,3-bis-[di-( 2-hydroxypropyl)-amino]-2-hydroxy-propane.

The following heterocyclic amines may also be used as tertiary aminesfor the process according to the invention:

l-isopropyl-, l-isobutyland l-neopentyl-Z-methylpiperidine,4-isopropyl-, 4-isobutyland 4-neopentyl- 2,6-dimethyl-morpholine,4-(2-hydroxypropyl)-2,6- dimethyl-morpholine,l,4-bis-(2-hydroxypropyl)-2,5- dimethyl-piperazine,1,4-bis-(isopropyl)-, 1,4-bis- (isobutyl)-andl,4-bis-(neopentyl)-2,5-dimethylpiperazine,l,3-bis-[2-methyl-piperidino-( 1 )]-2- hydroxy-propane,1,3-bis-[2,6-dimethyl-morpholino- (4)]-2-hydroxy-propane,1,2-bis-[4-isopropyl-2,5 dimethyl-piperazino( l )]-2-hydroxy-propane,l,2-bis- [4-isobutyl-2,5-dimethyl-piperazino-( l )1-2-hydroxypropane,l,2-bis-[4-neopentyl-2,S-dimethylpiperazino-( 1 )l-2-hydroxy-propane,1,2-bis-[4-(2- hydroxy-propyl)-2,5-dimethyl-piperazino-(1 )]-2-hydroxy-propane.

The following amines or mixtures thereof are preferably suitable for thequaternization of the dye bases (II) according to the invention:N-methylor N-ethylor diisopropylamine, N-n-propylor N-n-butyl-N,N-diisobutylamine, N-methylor N-ethyl-N,N- dicyclohexylamine,N,N,N-triisopropanolamine, N,N- diisobutyl-N-(2-hydroxypropyl)-amine,N-isobutylor N-isopropyl-N,N-bis-(2-hydroxy-propyl)-amine, N,N-tetraisopropyl-ethylene-diamine, 1,3-bis-(diisopropylamino)-2-hydroxy-propane, l,3-bis-[di-(2- hydroxy-propyl)-amino -2-hydroxy-propane, 1- isopropyI-Z-methyl-piperidine,4-isopropyl-2,6- dimethyl-morpholine, 4-(2-hydroxypropyl)-2,6-dimethyl-morpholine, 1,4-bis-(2-hydroxy-propyl)-2,5- dimethylpiperazine,l,3-bis-[2,6-dimethyl-morpholino- (4)1-2-hydroxy-propane,l,2-bis-[4-isopropyl-2,5- dimethyl-piperazino-( 1 )]-2-hydroxy-propane.

Of the above amines, the triisopropanolamine is especially to bementioned since it substantially increases the solubility of the dyebases (II) and particularly that of the quaternary dyestuffs (I) in thealkylating medium so that the amount of solvent can be decreased.

The tertiary amines used as alkaline agents are added in an amount of 550, preferably 15 25 mol percent, referred to the dye base (II) to bequaternized.

In German Published Pat. specification No. 1,132,135 it has beendescribed that tertiary amines of the type to be used according to theinvention can be used, due to their acid-binding action, as auxiliariesfor the alkylation of primary amines to give tertiary amines and fordehydrohalogenation reactions. In contradiction thereto, thequaternization reactions, such as those according to the invention,proceed with the addition of the alkylating agent on to the compound tobe quaternized, and thus, fundamentally, not with the splitting off ofprotons. It is therefore a surprising and novel fact that the degree ofthe reaction and the yield of the quaternization of the dye bases (II)to give the dyestuffs (I) are increased in the presence of theabovementioned tertiary amines. Rather the opposite was to be expected,viz. that the high basicity of the amines to be used according to theinvention would lead to the decomposition of the dyestuffs (I), asalready mentioned above, via their carbinol bases. The high basicity ofthese amines is characterized in that the pK value determinedpotentiometrically in a water-containing glycol monomethyl ether againstperchloric acid by means of a glass electrode calibrated in aqueousmedia lies above 5.5; (cf. S I-Iunig and M. Kiessel, J. prakt. Chemie[4], 5, 224 [1958]).

In German Pat. specification No. 1,205,638 the production has beendisclosed of dyestuffs of the general formula (IX) N-n-propyl-N,N-

in which A, R,, R R and R, have the meaning indicated for (IX),

with alkylating agents in the presence of acid-binding agents.Acid-binding agents are sodium hydrogen carbonate, potassium carbonate,sodium hydroxide, magnesium oxide, zinc oxide or calcium carbonate, theuse of magnesium oxide being preferred in the working Examples.

According to the process of German Pat. specification No. 1,205,638, twoalkyl groups are introduced stepwise into the dyestuff molecule (IX); Atfirst, the alkylation of a secondary amine nitrogen takes place to givea tertiary amine nitrogen. For the equivalent acid liberated in thisoperation according to experience, viz. in this step only, theacid-binding agent is required. The quaternization reaction following ina second step proceeds with the addition of an alkyl group on to thecompound to be quatemized, no protons being liberated in this process,so that for this second process step fundamentally no acid-binding agentis required according to the knowledge derived from the teachings ofGermanljat. specification No. 1,205,638. The fact that in this processacid-binding agents are present also in the second step, i.e., in thequaternization reaction,

has its only reason in that the acid-binding agent required in the firststep wasnqtremoved and the reaction completed in one single processstep. It can therefore not be concluded from German Pat. specificationbles the dyestuffs (I) to be obtained with a higher degree of puritythan could previously be achieved by additional purification andseparation operations according to the known quaternization process.

A particularly preferred embodiment of the present invention consists inthat the dye bases (11) are reacted at 50 90C, preferably at C, in awater-immiscible organic, aprotic solvent, such as benzene, toluene,xylene and halogenated derivatives thereof, especially chlorobenzene, aswell as anisole and chloroform, in the presenceof 5 50, preferably 15 25mol percent (referred to the dye base) triisopropanolamine with an'excess of dimethyl sulphate. The excess of dimethyl sulphate is someasured that the reaction mixture has an acid reaction upon theaddition of water. The quaternary dyestuff is isolated in known-manner,for example, by steam distillation and cooling of the aqueous solution,optionally with the addition of inorganic salts decreasing thesolubility.

1n the following Examples the parts by weight and the parts by volumeare in the ratio of kilogram to liter.

EXAMPLE 1 61.7 Parts by weight p-anisidine are introduced at 58C into amixture of 155 parts by volume hydrochloric acid (19.5 Be) and 250 partsby volume water, and the suspension of the hydrochloride is diazotizedat 0 3C with a solution of 35.1 parts by weight sodium nitrite in partsvolume of water. The excess of nitrite is destroyed with urea oramidosulphonic acid, and the diazo solution mixed at 5C with 86.7 partsby weight 1 ,3,3-trimethyl-2-methylene-indolenine. Coupling is effectedby the addition of 400 parts by volume of an aqueous solution containing200 g sodium acetate per liter. The coupling product is transformed intothe dye base by the addition of 440 parts by volume of a 2.5N causticsoda solution. Heating is continued for some time at 60C, the product isthen filtered off with suction, therelectrolytes are washed out withwater, and the product is dried at 70C in a vacuum until the weight isconstant. 155 Parts by weight of the anhydrous dye base of the formulaare obtained. Parts by weight of this dye base are dissolved in 1000parts by volume anhydrous chloroform, and 10 parts by weightN-ethyl-N,N- diisopropylamine are admixed. 50 Parts By volume of puredimethyl sulphate are added at 50 -.5-5C, and the mixture is kept at 5560C for a further 1 0 hours. The solvent is then distilled off withseam, the mixture. is made up with water to 1000 parts by volume, andthe dyestuff salted out with 85 partsby' weight sodium chloride. Thesuspension is allowed to cool to 20C and the precipitated dyestuff isfiltered off with" suction,

washed with a 10 percent-sodium chloridelsolution,

are obtained. The dyestuff dyes materials of polyacrylonitrile in goldenyellow shades. Only traces of the nonmethylated starting material can bedetected in the film chromatogram.

When in this Example the chloroform is replaced by equal amounts ofbenzene, toluene, xylene, chlorobenzene, o-dichlorobenzene or anisole,the dyestuff is obtained in approximately the same yield.

When the procedure is followed as described in the preceding Example,but replacing the p-anisidine there used as diazo component and the1,3,3-trimethyl-2- methylene-indoline used as coupling component byequivalent amounts of the components set out in the Table below,dyestuffs are obtained which correspond to the above formula and whichdye materials of polyacrylonitrile in the specified shades:

Shade of the Diazo component Coupling component quaternary dyestufl' onpolyacrylonitrile l-amino-4-methyl- 1,3,3-trimethyl-2- yellow benzenemethylene-indoline 53.7 Parts by weight p-toluidine are diazotized inconventional manner in dilute hydrochloric acid and coupled in anacetate-buffered medium with 86.7 parts by weight1,3,3-trimethyl-2-methylene-indoline. The coupling product is convertedinto the dye base with a dilute caustic soda solution withoutintermediate isolation. The dye base is washed with hot water untilneutral and dried at 60C is a vacuum. 144 Parts by weight of theanhydrous dye base Jill;

are obtained.

120 Parts by weight of this dye base are dissolved in 175 parts byvolume of anhydrous chlorobenzene while heating. 16.0 Parts by weightanhydrous triisopropanolamine are added and the mixture is heated to C.At this temperature there are added, while cooling, 52.8 parts by voluindimethyl sulphate and the mixture is kept at 80 85C for a further 10hours. The excess of dimethyl sulphate is then hydrolized with water,the chlorobenzene distilled off with steam, the mixture made up withwater to 1000 parts by volume, and the dyestuff is salted out with 85parts by weight sodium chloride. The suspension is allowed to cool to20C, the dyestuff is filtered off with suction, washed with a 10 percentsodium chloride solution to remove the mother liquor and the product isdried at 60C in a vacuum. 156 Parts by weight of the quaternary dyestuffof the formula are obtained.

Only traces of the non-methylated starting material can be detected inthe film chromatogram.

When the procedure is followed as described in the preceding Example,but the p-toluidine there used as diazo component and thel,3,3-trimethyl-2-methyleneindoline used as coupling component arereplaced by equivalent amounts of the components set out in the Tablebelow, dyestuffs are obtained which correspond to the above fonnula andwhich dye materials of polyacrylonitrile in the specified shades.

Shade of the quaternary dyestufl' on polyacrylonitrile Diazo componentCoupling component l-amino-3,4-dimethyl- 1,3,3-trimethyl-2- reddishyellow benzene methylene-indoline l-amino-4-chlororeddish yellow benzenel-amino-Z-methoxygreenish yellow benzene l-amino-2-methoxy-4- yellowmeth lbenzene l-amrno-Z-methoxy- 1,3,3-trimethyl-2- yellowl-amino-4-methyl- 1,3,3-trimethyl-5- yellowish orange benzenenitro-Z-methylenel-amino-4-methoxybenzene I -amino-4-methylbenzenel-amino-4-methoxybenzene l-aminol-methoxybenzene r 2',3-dimethyl-4-aminoazobenzene l-amino-4-methoxybenzene l-amino-4-methylbenzenel-amino-4-methylbenzene l-amino-4-methoxybenzene 4-aminoazobenzeneZ-aminonaphthalene aminobenzene indoline orange 1,3,3-trimethyl-5-yellow chloro-Z-methyleneindoline 1,3,3-trimethyl-7- yellowish orangechloro-Z-methylene- Z-methylene-indoline l-amino-4-methoxygolden yellowbenzene l-amino-4-ethoxygolden yellow benzene l-amino-3-chloro-4-yellowish orange rnethoxybenzene aminobenzene l ,3,3-trimethyl-5-reddish yellow methoxy-Z-methyleneindoline l-amino-4-methoxyyellowishorange benzene l-arnino-2,4-dimethoxyyellowish orange benzene4-arninoazobenzene orange EXAMPLE 3 120 Parts by weight of the anhydrousdye base of the formula prepared in the usual manner fromp-chloroaniline and l,3,3-trimethyl-2methylene-indoline, are dissolvedin 500 parts by volume anhydrous chlorobenzene and admixed 'with 12.4parts by weight l-,3-bis-[di-(2-hydroxy-proxy)-amino]-2-hydroxypropane.47.5 Parts by volume dimethyl sulphate are added at 70C and the mixtureis kept at 70C for a further 8 hours. The chlorobenzene is thendistilled off with steam, the aqueous dyestuff solution made up to 2000parts by volume and the dyestuff precipitated by cooling the solution to0C. The dyestuff is filtered off with suction, washed with a 2 percentsodium chloride solution at 0C to remove the mother liquor, and dried at60C in a vacuum. There are obtained 170 parts by weight of the Thedyestufi is obtained in the same yield when the l ,3-bis-[di-(2hydroxy-propyl)-amino]-2-hydro)rypropane is replaced by equivalentamounts of the following tertiary amines: methyl-, ethylandp-propyldiisopropyl-amine, n-propyland n-butyl-diisobutylamine,methyland ethyl-dicyclohexylamine, triisopropanolamine, diisobutyl-(2-hydroxypropyl)- amine, isobutyland isopropyl-bis-( 2-hydroxy-propyl)-amine, N,N'-tetraisopropyl-ethylene-diamine, 1,3-bis-(diisopropylamino)-2-hydroxy-propane, 1,3-bis-[di-( 2- hydroxy-propyl)-amino ]-2-hydroxy-propane lisopropyl-Z-methyl-piperidine,4-isopropyl-2,6- dimethyl-morpholine, 4-(2hydroxy-propyl)-2,6-dimethyl-morpholine, l,4-bis-(2-hydroxypropyl)-2,5- dimethylpiperazine,l,3-bis-[2,6-dimethyl-morpholino- (4 ]-2-hydroxy-propane, l,2-bis-[4-isopropyl-2,5- dimethyl-piperazino-( l )]-2-hydroxy-propane.

We claim:

1. Process for the production of basic dyestuff of the formula in whichR represents the residual constituent of a 5- or 6-membered heterocyclicring, R, denotes alkyl cycloalkyl, aralkyl or aryl, R denotes alkyl,cycloalkyl or alalkyl, A is a radical of the benzene or naphthaleneseries, and X is an anion, by quaternizing dye bases of the formula inwhich R, R, and A have the same meaning, as above, at the azo nitrogenlinked to A, with quaternizing agents wherein the quatemizing takesplace in the presence of alkaline agents, said alkaline agents beingtertiary amines selected from the group consisting of A. one wherein onesubstituent is selected from the group consisting of unbranched C alkyl,B- hydroxy propyl,

where n is 1-5 and the free N-valences contain, along with the other twosubstituents on the tertiary amine, substituents of the formula where mis 0 or 1 and when m is l,

R is alkyl with one to two carbon atoms;

R is alkyl with one to two carbon atoms or OH;

R is alkyl with one to two carbon atoms or H; and

when m is 0,

R is alkyl with one to two carbon atoms;

R is alkyl with one to two carbon atoms;

R is H;

and whenever R is H, R;, and R can be a single substituent forming withthe substituted carbon a member of the class cyclopentyl and cyclohexyl;and one of the heterocyclic tertiary amines of the class l-isopropyl-,l-isobutyland l-neopentyl-Z- methyl-piperidine, 4-isopr0pyl-,4-isobutyland 4- neopentyl- 2,6-dimethyl-morpholine, 4-( 2-hydroxypropyl)-2,6-dimethyl-morpholine, 1,4-bis-(2-hydroxypropyl)-2,5-dimethyl-piperazine, 1,4-bis- (isopropyl)-;i,4-bis-(isobutyl)-and 1,4-bis- (neopentyl)-2,5-dimethyl-piperazine,1,3-bis-[2- methyl-piperidino-( l )]-2-hydroxy-propane; l ,3-bis[2,6-dimethyl-morpholino-(4)]-2-hydroxypropane,l,2-bis-[4-isopropyl-2,S-dimethylpiperazino( 1)]2-hydroxy-propane,1,2-bis-[4- isobutyl-2,5-dimethyl-piperazino-( 1 )]-2-hydroxypropane,l,2-bis-[4-neopentyl-2,5-dimethylpiperazino-( l )]-2-hydroxy-propane,1,2-bis-[4-(2- hydroxy-propyl)-2,5-dimethyl-piperazino-( 1 )1-2-hydroxy-propane.

where A is a radical of the benzene or naphthalene series;

X is an anion;

R and R are short-chain alkyl or together for two linked short-chainalkyls; R and R are H or nonionic substituents; and

R and R are alkyl.

I I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Paten t No. 3718 1642 Dated February 22 12 Z:

Inventor(s) Klausf'Frj-edrich p 81; al

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 2, line '12, "bound" should read fou'nd---. Column 2, line 32,"end" should read ---and---; I Column 2, lin e 32 "base" should read---case-.

Column 2, line 35, "n" should read -m-" 7 Column 3, line 2 "Noethylshould, read N-'-ethyl---.

Column 4, line 21, "1,2-bis" shouldread --l,3-bis--.

Column 5, line 13 in the left formula, "-R" should read Column 5, line20, in the right formula, N should I Column 6, line 50, "By" should read--by---.

Column 6, line 53, "seam" should read ---steam-.

Signed and sealed this 3rd day of December 1974.

(SEAL) Attest;

McCOY M. GIBSON JR. c. MARSHALL DANN Arresting Officer Commissioner ofPatents FORM PO-1050 (1 O-69) I uscoMM-oc scan-ps9 Y v Q U,5. GOVERNMENTPRINTING OFFICE: I955 0-356-33

2. Process according to claim 1, characterized by using heterocyclicamines as substituted tertiary amines.
 3. Processes according to claim1, characterized by adding triisopropanolamine as tertiary amine. 4.Processes according to claim 1, characterized by adding thetriisopropanolamine in an amount of 5 - 50 mol percent, referred to thedye base to be quaternized.
 5. Process of claim 1 wherein the basicdyestuff is one of the formula